EP3152619B1 - Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques - Google Patents

Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques Download PDF

Info

Publication number
EP3152619B1
EP3152619B1 EP15747594.8A EP15747594A EP3152619B1 EP 3152619 B1 EP3152619 B1 EP 3152619B1 EP 15747594 A EP15747594 A EP 15747594A EP 3152619 B1 EP3152619 B1 EP 3152619B1
Authority
EP
European Patent Office
Prior art keywords
silicone
silicone film
groups
composition
sio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15747594.8A
Other languages
German (de)
English (en)
Other versions
EP3152619A1 (fr
Inventor
Masaaki Amako
Steven Swier
Haruna YAMAZAKI
Shin Yoshida
Makoto Yoshitake
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Toray Specialty Materials KK
Dow Silicones Corp
Original Assignee
Dow Corning Toray Co Ltd
Dow Corning Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Co Ltd, Dow Corning Corp filed Critical Dow Corning Toray Co Ltd
Publication of EP3152619A1 publication Critical patent/EP3152619A1/fr
Application granted granted Critical
Publication of EP3152619B1 publication Critical patent/EP3152619B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/54—Encapsulations having a particular shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0203—Containers; Encapsulations, e.g. encapsulation of photodiodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H01L2924/1815—Shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/005—Processes relating to semiconductor body packages relating to encapsulations

Definitions

  • Optical devices such as optical emitters, optical detectors, and optical amplifiers, may emit or receive light via an optical surface.
  • the optical surface may be or may include an electronic component or other component that may be sensitive to environmental conditions.
  • Certain optical devices such as optoelectronics generally, including light emitting diodes (LEDs), laser diodes, and photosensors, can include solid state electronic components that may be susceptible to electrical shorts or other damage from environmental conditions if not protected. Even optical devices that may not be immediately susceptible may degrade over time if not protected. Accordingly, films have been developed that provide at least some protection to the optical surface from environmental elements.
  • a protective film and a method for making such a protective film has been developed that may aid with light extraction from the optical device.
  • a process has been developed that creates an imprint on a silicone film that may improve light extraction from the optical device.
  • the imprint may be created during manufacturing of an optical assembly including the optical device and the silicone film by pressing a release liner having a related imprint onto the silicone film.
  • the silicone may be a hot melt silicone composition, as disclosed herein.
  • the pressing of the release liner may be during a heating process, such as during lamination.
  • the imprinting of the silicone film may be concurrent with the lamination of the silicone film to the optical device, resulting in a "one-time” production process, allowing the various components to be positioned with respect to one another in a fixture, such as a vacuum chamber, and the output producing the optical assembly.
  • FIG. 1 is a side profile of an optical assembly 100, in an example embodiment.
  • the optical assembly includes an optical device 102 and electrical leads 104 configured to provide electrical connectivity with the optical device 102, such as to provide a current to cause an LED to illuminate or to detect an output from an optical detector, in various example embodiments.
  • the optical device 102 includes an optical surface 106 from which light may either be emitted or detected.
  • the optical device 102 and the electrical leads 104 are encapsulated in a silicone film 108 that may, in various examples, be applied according to methods disclosed herein. While a silicone film made of various materials as disclosed herein with particularity, the silicone film 108 may be or include any suitable encapsulant that currently exists or that may be developed.
  • the silicone film 108 includes a distal surface 110 that is distal relative to the optical surface 106.
  • the distal surface 110 has been imprinted to create a pattern of protrusions 112.
  • the protrusions 112 may be bumps, corrugations, ridges, or other related projection. While the protrusions 112 as illustrated are in a pattern and are of regular shape, the protrusions 112 may be unpatterned and may be of irregular shape. Further, some or all of the protrusions 112 may be replaced with dimples, divots, or other indentations in the distal surface 110.
  • FIGs. 2A-2E are an illustration of a process for making the optical assembly 100, in an example embodiment. While the process is described with respect to the optical assembly 100, it is to be understood that the principles described herein may be applied to making any of a variety of optical assemblies.
  • a fixture 200 is made ready to receive the optical device 102 and the silicone film 108.
  • the fixture is a vacuum laminator, including a vacuum chamber 202, a membrane 204, and a heat source 206, such as a hotplate table.
  • the membrane 204 may be made of any suitable material including, but not limited to, rubber.
  • the fixture 200 does not necessarily include some or all of the components 202, 204, 206, and may instead include a mechanism for securing the optical device 102 and a pressing mechanism, such as a piston or other device that may be utilized to press an object into the silicone film 108, as will be disclosed herein.
  • the optical device 102 and the silicone film 108 are positioned within the fixture 200 and a release liner 208 positioned between the distal surface 110 of the silicone film 108 and the membrane 204.
  • An imprint surface 211 faces the distal surface 110 of the silicone film 108.
  • the release liner 208 is formed of plastic, such as ethylene tetrafluoroethylene (ETFE).
  • EFE ethylene tetrafluoroethylene
  • the silicone film 108 is not, at this point, attached or otherwise substantially secured to the optical device 102; such securing may come from a lamination or other process as disclosed herein.
  • the silicone film 108 may be loose with respect to the optical device 102 or may be lightly or otherwise non-permanently secured with respect to the optical device 102, such as with a fastener or adhesive.
  • the silicone film 108 may already be secured to the optical device 102, such as through a prior lamination process or other mechanism by which the silicone film 108 may be secured to the optical device 102 over the long term or permanently.
  • the fixture 200 is closed and a vacuum applied on both a first side 210 and a second side 212 of the membrane 204.
  • the membrane 204 serves to isolate the first and second sides 210, 212 with respect to one another, allowing a vacuum to be pulled independently on each side 210, 212.
  • the vacuum is released on the first side 210 while being maintained on the second side 212. Releasing the vacuum on the first side 210 causes the membrane 204 to press on the release liner 208, causing an imprint pattern on the release liner 208 to be imparted onto the silicone film 108.
  • the fixture 200 is held at vacuum for times from approximately four (4) minutes to approximately twenty (20) minutes and at a temperature of approximately one hundred thirty-five (135) °C. In some examples, the fixture is held at vacuum for approximately ten (10) minutes at a temperature of approximately one hundred fifty (150) °C.
  • the optical assembly 100 includes the silicone film 108 including the pattern as imparted from the release liner 208.
  • fixtures 200 may have capacity for multiple optical devices 102 and to produce multiple optical assemblies 100 concurrently.
  • the optical device 102 has dimensions of two hundred sixty (260) micrometers by five hundred eighty-five (585) micrometers and a thickness of ninety (90) micrometers.
  • the optical device 102 may be part of a board including multiple optical devices 102, such as a fifty (50) by fifty (50) millimeter board including one hundred (100) of the optical devices 102.
  • the fixture 200 may be configured to receive the entire board of optical devices 102.
  • the silicone film 108 is approximately four hundred (400) micrometers thick.
  • the silicone film 108 and/or the release liner 208 may be a single sheet to cover the optical surface106 of some or all of the optical devices 102 or may be discrete for each optical device 102.
  • the sheet may have a diameter of approximately thirty-five (35) millimeters.
  • the fixture 200 may be replaced or supplemented with any of a variety of pressing mechanisms that would allow for pressing the release liner 208 against the silicone film 108 to impart the imprint on the silicone film 108.
  • a pressing mechanism may act on the release liner 208 directly, i.e ., by leaving the optical device 102 and/or the silicone film 108 substantially stationary and actively pressing the release liner 208 against the silicone film 108, may act on the optical device 102 and/or the silicone film 108 directly, i.e ., by leaving the release liner 208 substantially stationary and actively pressing the optical device 102 and/or the silicone film 108 against the release liner, or may act on both the release liner 208 and the optical device 102 and/or the silicone film 108 directly.
  • the fixture 200 does not include a heat source 206 and does not necessarily laminate or otherwise secure or attach the silicone film 108 to the optical device 102. Rather, in various examples, the fixture 200 may simply be a press for imparting the imprint onto the silicone film 108.
  • FIGs. 3A and 3B are top profiles of example release liners 208A and 208B, respectively, in various example embodiments.
  • the illustrated release liners 208A, B are presented as representative examples and are nonlimiting.
  • the release liner 208A includes a regular pattern of pillars 300 on a surface 302 that is configured to face the distal surface 110 of the silicone film 108 when the silicone film 108 and the release liner 208A are positioned in the fixture 200.
  • the release liner 208A may be utilized to make the protrusions 112 of the silicone film 108 as illustrated in FIG. 1 .
  • the release liner 208A is formed of a cyclic olefin polymer (COP) having a phi of approximately two hundred thirty (230) nanometers, a pillar height of approximately two hundred (200) nanometers, a pillar pitch of approximately four hundred (400) nanometers, and a film thickness of approximately 200 micrometers.
  • COP cyclic olefin polymer
  • the release liner 208A When the release liner 208A is used, the release liner 208A may be pressed against the silicone film 108 in the vacuum for approximately twenty (20) minutes at one hundred thirty-five (135) °C.
  • the resultant optical assembly 100 may have protrusions 112 of approximately one hundred twenty (120) to approximately one hundred sixty (160) nanometers in depth.
  • the release liner 208B includes a micro mesh pattern 304.
  • the micro mesh pattern has a mesh count of three hundred twenty-five and a wire diameter of approximately two hundred eighty (280) micrometers.
  • the micro mesh pattern 304 may be formed by hot-pressing a metal micro mesh onto the material of the release liner 208B, as disclosed herein, such as for one (1) minute at one hundred fifty (150) °C. Additionally or alternatively, the release liner 208B may be the metal micro mesh and may be applied directly to the silicone film 108, as disclosed herein.
  • a release liner 208 includes a random or otherwise irregular arrangement of cavities configured to create a random arrangement of protrusions 112 on the silicone film 108.
  • the release liner may include a moth-eye pattern and be formed of metal.
  • the cavities may have a depth of approximately two hundred and twelve (212) nanometers and a pitch of approximately one hundred thirty (130) nanometers.
  • An optical assembly 100 including a silicone film 108 with a resultant arrangement of protrusions 112 may, in various examples, have a LOP of approximately 1,772 milliwatts in comparison with a LOP of the optical device 102 without the silicone film 108 of approximately 1,740 milliwatts, or an improvement of approximately 1.8 percent.
  • FIG. 4 is a flowchart for making an optical assembly, in an example embodiment.
  • the optical assembly is the optical assembly 100. Additionally or alternatively, the method may be applied to making any suitable optical assembly.
  • an optical device is secured in a fixture, the optical device having an optical surface, wherein a silicone film is positioned with respect to the optical surface, the silicone film having a distal surface relative to the optical surface.
  • the silicone film comprises a silicone-containing hot melt composition.
  • the silicone-containing hot melt composition comprises an organosiloxane block copolymer.
  • a thickness of the silicone film is greater than a thickness of the optical device.
  • a release liner is positioned with a liner surface facing the silicone film, the release liner including an imprint on the liner surface.
  • the imprint of the release liner comprises at least one pillar or one cavity having a primary dimension from approximately ten (10) nanometers to approximately five hundred (500) micrometers.
  • the imprint of the release liner comprises a plurality of substantially equally sized cavities or pillars. the cavities form a substantially regular pattern.
  • the release liner is comprised of at least one of a metal and a plastic.
  • the release liner is pressed against the silicone film, thereby causing the imprint of the release liner to be imparted to the distal surface of the silicone film creating a surface imprint in the distal surface.
  • the fixture includes a vacuum chamber and a membrane and wherein pressing the release liner comprises creating, with the vacuum chamber, a pressure difference between a first side of the membrane and a second side of the membrane and cause the membrane to press the release liner against the silicone film.
  • the material of the membrane Organic film, patterned film and metal film, release liner are applicable as the membrane.
  • heat is applied with a heat source to the silicone film to laminate the silicone film to the optical device.
  • applying heat is at least partially concurrent with pressing the release liner.
  • the resin when part of a thermoset resin in an unreacted A-stage is reacted, the resin can enter a B-stage in which part of the crosslinkable functional groups are reacted. In A-stage and B-stage, the resin can be reduced in viscosity, softened, or liquefied via heating. If the reaction continues, the resin enters a completely cured C-stage.
  • the curable silicone composition according to the various embodiments of the present invention is in a state corresponding to "A-stage" or "B-stage", and, in particular, is thermoplastic because a curable silicone composition comprising a component that is solid at room temperature is used. It is therefore possible to "plastically" work the hot-melt curable silicone composition for laminating according to the present invention.
  • hot-melt and hot-meltable generally refer to substances that are solid at room temperature (25°C) but soften or melt when heated, entering a viscous, fluid, or liquid state, such as hot-melt adhesives typified by ethylene vinyl acetate-based adhesives.
  • compositions of the various embodiments of the present invention is a "hot-melt” composition or a silicone-containing "hot melt” composition, and therefore can be solid at room temperature (25°C).
  • room temperature 25°C
  • the form of the composition of the present invention for example, it may take the form of a powder, granules, pellets, tablets, a film, or a sheet.
  • compositions of the various embodiments of the present invention have, in some embodiments, a type A durometer hardness of at least 50 at 25°C as defined by JIS K 6253, at least 60 or at least 70.
  • the composition of the present invention is, in some embodiments, either fluid at 100°C or has a type A durometer hardness at 100°C of no more than 10, no more than 5 or no more than 1. If the composition is fluid at 100°C, there is no particular limitation upon the viscosity thereof; a minimum of 0.01 Pa•s or 0.1 Pa•s.
  • the maximum viscosity if the composition is fluid at 100°C can be 1,000 Pa•s, 100 Pa•s or 10 Pa•s.
  • the minimum torque value from immediately after closing the die (cure time: 0 seconds) until 300 seconds, when measuring at a temperature of at least 100°C using, e.g., a moving die rheometer (MDR) according to JIS K 6300-2 "Rubber, unvulcanized -- Physical property -- Part 2: Determination of cure characteristics with oscillating curemeters", is no more than 1 kgf•cm or no more than 0.1 kgf•cm.
  • MDR moving die rheometer
  • the composition of the present invention can therefore be favorably used as a thermoplastic film or sheet that deforms when heated.
  • compositions of the various embodiments of the present invention are capable of undergoing crosslinking and curing when heated.
  • the minimum heating temperature is, in some embodiments, about 50°C, about 80°C or about 100°C.
  • the maximum heating temperature is, in some embodiments, about 200°C or about 150°C.
  • the compositions of the various embodiments of the present invention have curing properties such that the time from immediately after beginning measurement until a torque of 1 kgf•cm is reached, when measuring in a heating temperature range using a moving die rheometer (MDR), is no more than 5 minutes, no more than 3 minutes or no more than 1 minute. Measurement can be performed using the MDR according to a method complying with JIS K 6300-2 "Rubber, unvulcanized -- Physical property -- Part 2: Determination of cure characteristics with oscillating curemeters".
  • compositions of the various embodiments of the present invention itself, or the cured product thereof have, in some embodiments, a refractive index of at least 1.40.
  • the refractive index can be measured using, for example, an Abbe refractometer. In such cases, the wavelength of the light source for the Abbe refractometer can be altered to measure a refractive index at a desired wavelength.
  • the curable silicone composition or cured product thereof has, in some embodiments, a refractive index (at 25°C) at a visible light wavelength (at 589 nm) of 1.40 or greater, from about 1.50 to about 1.70 or from about 1.55 to about 1.60.
  • the composition of the present invention itself or the cured product thereof can have a light transmission rate (at 25°C) of at least about 80%, at least about 90% or at least about 95% (e.g. from about 80% to about 100%, about 80% to about 95%, about about 90% to about 100% or about 95% to about 100%).
  • This light transmission rate can be calculated, for example, by measuring the composition of the present invention or the cured product thereof using a light transmission rate (at 25°C) spectrophotometer using a light path distance of 0.2 cm and a wavelength of 450 nm.
  • the composition of the present invention is in some embodiments, for example, an A-stage silicone composition that comprises a solid organopolysiloxane and is solid at room temperature, or a B-stage silicone composition that can be crosslinked and cured via a hydrosilylation reaction.
  • the B-stage composition according to the present invention is, in some embodiments, partially crosslinked via a hydrosilylation reaction, forms a solid with high hardness, specifically, a hard rubber-like state, at room temperature, and either takes on a significantly softened form, specifically, a soft rubber-like state, or liquefies at high temperatures, such as 100°C.
  • compositions of the present invention can be crosslinked and cured via a hydrosilylation reaction.
  • compositions are selected from the group consisting of:
  • the unreacted hydrosilylation curable (reactive) silicone composition comprises:
  • component (A) there is no limitation upon the molecular structure of component (A); examples include a straight, partially branched straight, branched, dendritic, reticulated, or cyclic structure.
  • Non-limiting examples of the alkenyl group in component (A) include straight or branched alkenyl groups having from 2 to 10 carbons (e.g., 2 to 8 carbons, 2 to 5 carbons or 2 to 4 carbons), such as vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, pentenyl groups, and hexenyl groups.
  • a vinyl group or allyl group is preferable, and a vinyl group is more preferable.
  • Component (A) can optionally have on average at least three alkenyl groups in a molecule.
  • component (A) can comprise a monovalent hydrocarbon group bonded to a silicon atom and having from 1 to 20 carbon atoms.
  • the monovalent hydrocarbon groups include alkyl groups having from 1 to 20 carbon atoms, aryl groups having from 6 to 20 carbon atoms, and aralkyl groups having from 7 to 20 carbon atoms.
  • alkyl groups having from 1 to 20 carbon atoms examples include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, cyclopentyl groups, hexyl groups, cyclohexyl groups, heptyl groups, and other straight, branched, or cyclic alkyl groups.
  • the monovalent hydrocarbon group is preferably a methyl group.
  • aryl groups having from 6 to 20 carbon atoms examples include phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and anthracenyl groups.
  • Examples of the aralkyl groups having from 7 to 20 carbon atoms include benzyl groups, phenethyl groups, and phenylpropyl groups.
  • Part of the hydrogen atoms of the monovalent hydrocarbon group may be partially substituted by halogen atoms, hydroxyl groups, or epoxy groups.
  • Dimethylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, copolymers of dimethylsiloxane and methylvinylsiloxane capped at both molecular terminals with trimethylsiloxy groups, and copolymers of siloxane units represented by the formula SiO 4/2 and siloxane units represented by the formula (CH 2 CH)(CH 3 ) 2 SiO 1/2 are preferred.
  • Component (A) can be, in some embodiments, a phenyl group-containing organopolysiloxane represented by the following average unit formula: (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e wherein:
  • Examples of the alkyl group of R 1 include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, and hexyl groups.
  • Examples of the cycloalkyl group of R 1 include cyclopentyl groups and cyclohexyl groups.
  • Examples of the alkenyl group of R 1 include vinyl groups, allyl groups, butenyl groups, pentenyl groups, and hexenyl groups.
  • R 1 represents a phenyl group.
  • the phenyl group content is in a range of 60 to 80 mol% or from 65 to 80 mol%. While not wishing to be bound by any particular theory, it is believed that there can be insufficient softening of the composition of the various embodiments of the present invention at high temperatures if the phenyl group content is less than the minimum value of the range given herein. There can also be a loss of transparency and/or reduction in mechanical strength of the composition of the various embodiments of the present invention, or a cured product thereof, if the phenyl group content exceeds the maximum value of the range given herein.
  • R 1 represents an alkenyl group.
  • the alkenyl group content is in a range of 10 to 20 mol%. While not wishing to be bound by any particular theory, it is believed that if the alkenyl group content is less than the minimum value of the range given herein, can be insufficiently hard at room temperature. In some instances, if the alkenyl group content exceeds the maximum value of the range given herein, there can be insufficient softening of the composition of the present invention at high temperatures.
  • alkyl group of R 2 examples include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, and hexyl groups, with methyl groups and ethyl groups being preferable.
  • a is a number indicating the fraction of siloxane units represented by the general formula: R 1 3 SiO 1/2
  • "a" is a number satisfying 0 ⁇ a ⁇ 0.2, and preferably 0 ⁇ a ⁇ 0.1. While not wishing to be bound by any particular theory, it is believed that the composition of the present invention can be insufficiently hard at room temperature if "a" exceeds the maximum value of the range given herein.
  • "b” is a number indicating the fraction of siloxane units represented by the general formula: R 1 2 SiO 2/2
  • "b" is a number satisfying 0.2 ⁇ b ⁇ 0.7, and preferably 0.4 ⁇ b ⁇ 0.7. While not wishing to be bound by any particular theory, it is believed that insufficient softening of the composition of the present invention at high temperatures can result if "b" is less than the minimum value of the range given herein. In some instances, there can be insufficient hardness of the composition of the present invention at room temperature if "b" exceeds the maximum value of the range given herein.
  • c is a number indicating the fraction of siloxane units represented by the general formula: R 1 SiO 3/2
  • "c" is a number satisfying 0.2 ⁇ c ⁇ 0.6, and preferably 0.3 ⁇ c ⁇ 0.6. While not wishing to be bound by any particular theory, it is believed that insufficient hardness of the composition of the present invention at room temperature can result if "c" is less than the minimum value of the range given herein. In some instances, insufficient softening of the composition of the present invention at high temperatures can result if "c" exceeds the maximum value of the range given herein.
  • d is a number indicating the fraction of siloxane units represented by the general formula: SiO 4/2
  • d is a number satisfying 0 ⁇ d ⁇ 0.2, and preferably 0 ⁇ d ⁇ 0.1. While not wishing to be bound by any particular theory, it is believed that insufficient softening of the composition of the present invention at high temperatures can result if "d" exceeds the maximum value of the range given herein.
  • component (A) can be a mixture of:
  • component (A-1) is the primary component of the composition, and can be the component already described as component (A).
  • component (A-2) is a component for improving the ease of handling and workability of the composition and modifying the hardness thereof at room temperature, and is preferably a phenyl group-containing organopolysiloxane represented by the following general formula: R 3 3 SiO(R 3 2 SiO) m SiR 3 3 wherein:
  • Examples of the alkyl group of R 3 include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, and hexyl groups.
  • Examples of the cycloalkyl group of R 3 include cyclopentyl groups and cyclohexyl groups.
  • Examples of the alkenyl group of R 3 include vinyl groups, allyl groups, butenyl groups, pentenyl groups, and hexenyl groups.
  • R 3 represents a phenyl group.
  • the phenyl group content is in a range of 40 to 70 mol% or from 40 to 60 mol%. While not wishing to be bound by any particular theory, it is believed that insufficient softening of the composition of the present invention at high temperatures can result if the phenyl group content is less than the minimum value of the range given herein. In other embodiments, loss of transparency and/or reduction in mechanical strength in the cured composition of the present invention can result if the phenyl group content exceeds the maximum value of the range given herein.
  • at least one of R 3 is an alkenyl group. While not wishing to be bound by any particular theory, it is believed that non-incorporation of the component into the crosslinking reaction and bleeding out of the composition of the present invention can result if there is no alkenyl group.
  • m is an integer in a range of 5 to 100, and preferably is an integer in a range of 10 to 50. While not wishing to be bound by any particular theory, it is believed that the mechanical strength of the composition of the present invention can be diminished if “m” is less than the minimum value of the range given herein. In some embodiments, the ease of handling and workability of the composition of the present invention can be diminished if "m" exceeds the maximum value of the range given herein.
  • component (B) functions as a crosslinking agent having a viscosity at 25oC in a range of 1 to 1,000 mPa•s, in a range of 1 to 500 mPa•s or in a range of 1 to 100 mPa•s.
  • component (B) there is no limitation upon the molecular structure of component (B); examples include a straight, partially branched straight, branched, dendritic, reticulated, or cyclic structure.
  • Component (B) may optionally have at least three silicon-bonded hydrogen atoms in a molecule.
  • component (B) can have a monovalent hydrocarbon group bonded to a silicon atom and having from 1 to 20 carbon atoms.
  • the monovalent hydrocarbon groups include alkyl groups having from 1 to 20 carbon atoms, aryl groups having from 6 to 20 carbon atoms, and aralkyl groups having from 7 to 20 carbon atoms.
  • alkyl groups having from 1 to 20 carbon atoms in component (B) include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, cyclopentyl groups, hexyl groups, cyclohexyl groups, heptyl groups, and other straight, branched, or cyclic alkyl groups.
  • the monovalent hydrocarbon group is preferably a methyl group.
  • Examples of the aryl groups having from 6 to 20 carbon atoms include phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and anthracenyl groups.
  • Examples of the aralkyl groups having from 7 to 20 carbon atoms include benzyl groups, phenethyl groups, and phenylpropyl groups.
  • Part of the hydrogen atoms of the monovalent hydrocarbon group may be partially substituted by halogen atoms, hydroxyl groups, or epoxy groups.
  • component (B) examples include methylhydrogenpolysiloxane capped at both molecular terminals with trimethylsiloxy groups, copolymer of dimethylsiloxane and methyl hydrogensiloxane capped at both molecular terminals with trimethylsiloxy groups, methylhydrogenpolysiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups, copolymer of dimethylsiloxane and methylhydrogensiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups, cyclic methylhydrogensiloxane, cyclic dimethylsiloxane-methylhydrogensiloxane copolymer, copolymers of siloxane units represented by the formula (CH 3 ) 3 SiO 1/2 , siloxane units represented by the formula H(CH 3 ) 2 SiO 1/2 and siloxane units represented by the formula SiO 4/2 , copolymers of siloxane units represented by the formula
  • from 30 to 70 mol% of the monovalent hydrocarbon groups of component (B) are phenyl groups. While not wishing to be bound by any particular theory, it is believed that insufficient softening of the composition of the present invention at high temperatures can result if the phenyl group content is less than the minimum value of the range given herein. Loss of transparency and/or reduction in mechanical strength in the cured composition of the present invention can result if the phenyl group content exceeds the maximum value of the range given herein.
  • component (B) is an organotrisiloxane represented by the following general formula: (HR 4 2 SiO) 2 SiR 4 2
  • R 4 is a phenyl group, or an alkyl group or cycloalkyl group having from 1 to 6 carbon atoms.
  • alkyl group of R 4 include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, and hexyl groups.
  • cycloalkyl group of R 4 include cyclopentyl groups and cyclohexyl groups.
  • the phenyl group content of R 4 is in a range of 30 to 70 mol%.
  • component (B) content is an amount such that the molar ratio of silicon atom-bonded hydrogen atoms therein to the total amount of alkenyl groups in component (A) is in a range of 0.2 to 4, preferably from 0.5 to 2, more preferably from 0.8 to 1.8, and still more preferably from 0.5 to 1.5. While not wishing to be bound by any particular theory, it is believed that insufficient hardness of the composition of the present invention at room temperature can result if the content of component (B) is outside the range given herein.
  • Component (C) is a hydrosilylation reaction catalyst for causing or promoting a hydrosilylation reaction between the alkenyl groups of component (A) and the silicon atom-bonded hydrogen atoms of component (B).
  • component (C) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Platinum-based catalysts are preferred due to the ability to promote curing of the present composition.
  • the platinum-based catalyst include a platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex and a platinum-carbonyl complex, with a platinum-alkenylsiloxane complex being particularly preferred.
  • alkenylsiloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes having part of the methyl groups of these alkenylsiloxane substituted by ethyl groups, or phenyl groups, and alkenylsiloxanes having vinyl groups of these alkenylsiloxane substituted by allyl groups, or hexenyl groups.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is particularly preferred due to high stability of the platinum-alkenylsiloxane complex. Due to the ability for improving the stability of the platinum-alkenylsiloxane complexes, combination is recommended of the platinum-alkenylsiloxane complexes with organosiloxane oligomers such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, or 1, 3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxane, or dimethylsiloxane oligomers.
  • component (C) content there is no particular limitation upon component (C) content as long as it is an amount sufficient to effect or promote a hydrosilylation reaction between the alkenyl groups of component (A) and the silicon atom-bonded hydrogen atoms of component (B), but it is, in some embodiments, an amount such that the amount of metal elements in terms of mass units in the component with respect to the composition prior to partial curing is within a range from 0.01 to 500 ppm, from 0.01 to 100 ppm or from 0.01 to 50 ppm. While not wishing to be bound by any particular theory, it is believed that the composition can exhibit a tendency not to sufficiently crosslink if the amount of component (C) is less than the lower limit of the range described herein. In some instances, discoloration of the composition according to the present invention can occur if the amount exceeds the upper limit of the range described herein.
  • the hydrosilylation curable silicone composition (2) obtained by partially cross-linking an unreacted hydrosilylation curable silicone composition can be obtained by stopping a hydrosilylation reaction at from 50 to 95% conversion of a hydrosilylation reactive silicone composition comprising:
  • Components (A) to (C) described herein can be used for components (D) to (F), respectively.
  • the viscosity of the unreacted hydrosilylated curable silicone composition can be in a range of 100 to 1,000,000 mPa•s or from 500 to 50,000 mPa•s. While not wishing to be bound by any particular theory, it is believed that the mechanical strength of the composition of the present invention can be diminished if the viscosity is less than the minimum value of the range given here. In some instances, the ease of handling and workability of the composition of the present invention can be diminished if the viscosity exceeds the maximum value of the range given herein.
  • Component (D) comprises, in some embodiments, a mixture of:
  • Component (D-2) content may be an amount in a range of 0 to 15 parts by weight per 100 parts by weight of component (D-1), or an amount in a range of 0 to 10 parts by weight. While not wishing to be bound by any particular theory, it is believed that insufficient softening of the composition of the present invention at high temperatures can result if component (D-2) content exceeds the maximum value of the range given herein.
  • the "conversion" of the hydrosilylation reaction is the degree of consumption of the alkenyl groups of component (D) or the silicon atom-bonded hydrogen atoms of component (E); for example, 80% conversion can indicate that 80% of the alkenyl groups of component (D) or the silicon atom-bonded hydrogen atoms of component (E) have been consumed in the hydrosilylation reaction.
  • the unreacted hydrosilylation curable silicone composition can be heated for a comparatively short time to yield a conversion of from 50 to 95%.
  • the heating temperature is, in some embodiments, from 50 to 200°C or from 80 to 150°C.
  • the heating time is, in some embodiments, from 1 to 20 minutes or from 5 to 15 minutes. Conversion can be measured against, for example, the heat-generating peak area obtained by measuring the unreacted composition via differential scanning calorimetry (DSC) as a reference.
  • DSC differential scanning calorimetry
  • the hydrosilylation curable silicone composition (3) contains:
  • Components (A), (B), (C), and (E) described above can be used for the components (G-1), (G-2), (G-3), and (H), respectively.
  • one or more of the following conditions is satisfied:
  • the monovalent hydrocarbon group and alkenyl group are as described herein.
  • Examples of the monovalent hydrocarbon groups not comprising an aliphatic unsaturated bond include alkyl groups having from 1 to 20 carbon atoms, aryl groups having from 6 to 20 carbon atoms, and aralkyl groups having from 7 to 20 carbon atoms.
  • alkyl groups having from 1 to 20 carbon atoms examples include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, cyclopentyl groups, hexyl groups, cyclohexyl groups, heptyl groups, and other straight, branched, or cyclic alkyl groups.
  • the monovalent hydrocarbon group is preferably a methyl group.
  • aryl groups having from 6 to 20 carbon atoms examples include phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and anthracenyl groups.
  • Examples of the aralkyl groups having from 7 to 20 carbon atoms include benzyl groups, phenethyl groups, and phenylpropyl groups.
  • Part of the hydrogen atoms of the monovalent hydrocarbon group may be partially substituted by halogen atoms, hydroxyl groups, or epoxy groups.
  • the relative amounts of components (G-1) and (G-2) are adjusted so that the ratio of the total molar concentration of silicon atom-bonded hydrogen atoms in component (G-2) to the total molar concentration of alkenyl groups in component (G-1) is in a range of 0.3 to 0.9; thus, the crosslinked product obtained by hydrosilylating the unreacted hydrosilylation reactive silicone composition (G) has alkenyl groups not consumed in the hydrosilylation reaction. It is therefore possible to further crosslink and cure the hydrosilylation curable silicone composition (3) via a hydrosilylation reaction as a result of the presence of component (H).
  • the composition of the present invention can comprise, as an optional component, a reaction retarder such as ethynyl hexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, or another other alkyne alcohol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, or another enyne compound; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, or benzotriazole.
  • a reaction retarder content e.g., in a range of 1 to 5,000 ppm with respect to the weight of the composition.
  • the composition of the present invention can also comprise an adhesion promoter in order to improve bondability to various substrates.
  • adhesion promoters include, but are not limited to: organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group (e.g., a trimethoxysiloxy group or triethoxysiloxy group) or a trialkoxysilylalkyl group (e.g., a trimethoxysilylethyl group or triethoxysilylethyl group) and a hydrosilyl group or alkenyl group (e.g., a vinyl group or allyl group); organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group or trialkoxysilylalkyl group, and a meth
  • adhesion promoters include: vinyl trimethoxysilane, allyl trimethoxysilane, allyl triethoxysilane, hydrogen triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, reaction products of 3-glycidoxypropyl triethoxysilane and 3-aminopropyl triethoxysilane, condensation reaction products of silanol group chain-terminated methylvinylsiloxane oligomers and 3-glycidoxypropyltrimethoxysilane, condensation reaction products of silanol group chain-terminated methylvinylsiloxane oligomers and 3-glycidoxypropyl
  • composition of the present invention can further comprise, as optional components, an organopolysiloxane other than components (A) to (H); an inorganic filler such as silica, glass, alumina, or zinc oxide; a fine-powdered organic resin such as polymethacrylate resin; a heat resistance agent; a dye; a pigment; a phosphor; a flame resistance agent; or a solvent; to the extent that such optional components do not adversely affect, among other features, the optical and physical properties of the compositions of the various embodiments of the present invention.
  • an organopolysiloxane other than components (A) to (H) an inorganic filler such as silica, glass, alumina, or zinc oxide
  • a fine-powdered organic resin such as polymethacrylate resin
  • a heat resistance agent such as a dye; a pigment; a phosphor; a flame resistance agent; or a solvent
  • the composition of the various embodiments of the present invention comprise at least one type of organopolysiloxane block copolymer.
  • hydrocarbon groups examples include the monovalent hydrocarbon groups described herein.
  • the organopolysiloxane block copolymer has a weight average molecular weight (Mw) of at least 20,000 g/mole, alternatively a weight average molecular weight of at least 40,000 g/mole, alternatively a weight average molecular weight of at least 50,000 g/mole, alternatively a weight average molecular weight of at least 60,000 g/mole, alternatively a weight average molecular weight of at least 70,000 g/mole, or alternatively a weight average molecular weight of at least 80,000 g/mole.
  • Mw weight average molecular weight
  • the organosiloxane block copolymer has a weight average molecular weight (Mw) of from about 20,000 g/mole to about 250,000 g/mole or from about 100,000 g/mole to about 250,000 g/mole, alternatively a weight average molecular weight of from about 40,000 g/mole to about 100,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 100,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 80,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 70,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 60,000 g/mole.
  • Mw weight average molecular weight
  • the weight average molecular weight of the organosiloxane block copolymer is from 40,000 to 100,000, from 50,000 to 90,000, from 60,000 to 80,000, from 60,000 to 70,000, of from 100,000 to 500,000, of from 150,000 to 450,000, of from 200,000 to 400,000, of from 250,000 to 350,000, or from 250,000 to 300,000 g/mole.
  • the organosiloxane block copolymer has a weight average molecular weight of from 40,000 to 60,000, from 45,000 to 55,000, or about 50,000 g/mole.
  • the composition comprising at least one type of organopolysiloxane block copolymer has a refractive index of at least 1.4 as determined using ASTM D542. In some embodiments, the composition comprising at least one type of organosiloxane block copolymer has a refractive index from about 1.4 to about 2.5, e.g., from about 1.5 to about 2.5; from about 1.7 to about 2.4; from about 1.4 to about 1.7; or from about 1.9 to about 2.3.
  • organopolysiloxane block copolymers examples include those disclosed in WO2012/040457 , WO2012/040453 , WO2012/040367 , WO2012/040305 , and WO2012/040302 .
  • the present invention relates to a silicone film comprising the composition of the present invention. At least 20 weight% of the silicone film of the present invention is constituted by the composition, at least 50 weight%, at least 70 weight%, at least 90 weight% or, in some embodiments, the film is constituted only by the composition.
  • composition and silicone film according to the present invention can comprise at least one type of phosphor.
  • a combination of two or more types of phosphors may also be used. It is thereby possible, if, for example, the composition or silicone film according to the various embodiments of the present invention is used to seal a light-emitting body such as an LED, allowing the wavelength of the emitted light to be converted, and the color of the light emitted by the LED to be adjusted.
  • a light-emitting body such as an LED
  • the phosphor is comprised within the sheet, the LED or other light-emitting body can easily be positioned, and the color thereof easily adjusted. Compression molding or laminating can also be performed immediately after adjusting the light emission color to efficiently obtain a seal.
  • the phosphor is not present in a liquid, there is no settling of the phosphor during storage which could lead to a non-uniform concentration distribution.
  • the phosphor may be any known phosphor, and, in order to increase the thickness of the single-layer sheet and favorably convert wavelengths, the minimum content of phosphor is, in some embodiments, at least 0.01 weight% with respect to the total weight of the composition or silicone film according to the present invention, at least 0.1 weight% or at least 1 weight%. In other embodiments, to convert wavelengths while reducing the thickness of the single-layer sheet, the minimum content of phosphor is, in some embodiments, 10 weight%, 20 weight% or 50 weight%. In still other embodiments, to convert wavelengths while reducing the thickness of the single-layer sheet, the maximum content of phosphor is, in some embodiments, 95 weight%, 90 weight%, 80 weight% or 50 weight%.
  • the maximum content of phosphor is 30 weight%, 20 weight% or 10 weight%.
  • the phosphor has a particle size range as measured, for example, in particle distribution measurement via a laser photodiffraction method utilizing a CILAS laser measurement device, such that particle size is, in some embodiments, at least 10 nm, from 10 nm to 100 ⁇ m or 100 nm to 30 ⁇ m.
  • the thickness of the silicone film according to the present invention for example, from 10 ⁇ m to 10 mm or from 20 ⁇ m to 5 mm.
  • the phosphor may be any phosphor that is capable of absorbing, for example, light from an LED and converting the light to a different wavelength.
  • Examples include one or more of nitride and oxynitride phosphors primarily activated by a lanthanide element such as europium or cerium, alkaline earth halogen apatite phosphor primarily activated by a lanthanide such as europium or a transition metal element such as manganese, alkali earth metal boric acid halogen phosphors, alkali earth metal aluminate phosphors, alkaline earth silicate phosphors, alkaline earth sulfide phosphors, alkaline earth thiogallate phosphors, alkaline earth silicon nitride phosphors, germanate phosphors, rare earth luminate phosphors primarily activated by a lanthanide element such as cerium, rare earth silicate phosphors, organic and organic complex
  • nitride phosphor primarily activated by a lanthanide element such as europium or cerium includes M 2 Si 5 N 8 :Eu (wherein M is at least one selected from strontium, calcium, barium, magnesium and zinc).
  • M 2 Si 5 N 8 :Eu examples include MSi 7 N 10 :Eu, M 1.8 Si 5 O 0.2 N 8 :Eu, and M 0.9 Si 7 O 0.1 N 10 :Eu (wherein M is at least one selected from strontium, calcium, barium, magnesium and zinc).
  • An example of the oxynitride phosphor primarily activated by a lanthanide element such as europium or cerium includes MSi 2 O 2 N 2 :Eu (wherein M is at least one selected from strontium, calcium, barium, magnesium and zinc).
  • alkaline earth halogen apatite phosphor primary activated by a lanthanide element such as europium or a transition metal element such as manganese includes M 5 (PO 4 ) 3 X:R (wherein M is at least one selected from strontium, calcium, barium, magnesium and zinc; X is at least one selected from fluorine, chlorine, bromium, and iodine; and R is at least one selected from europium, manganese, or europium and manganese).
  • alkali earth metal boric acid halogen phosphor includes M 2 B 5 O 9 X:R (wherein M is at least one selected from strontium, calcium, barium, magnesium and zinc; X is at least one selected from fluorine, chlorine, bromium, and iodine; and R is at least one selected from europium, manganese, or europium and manganese).
  • alkali earth metal aluminate phosphor examples include SrAl 2 O 4 :R, Sr 4 Al 14 O 25 :R, CaAl 2 O 4 :R, BaMg 2 Al 16 O 27 :R, BaMg 2 Al 16 O 12 :R, BaMgAl 10 O 17 :R (wherein R is at least one selected from europium, manganese, or europium and manganese).
  • alkaline earth sulfide phosphors examples include La 2 O 2 S:Eu, Y 2 O 2 S:Eu, and Gd 2 O 2 S:Eu.
  • rare earth aluminate phosphor primarily activated by a lanthanide element such as cerium includes a YAG phosphor represented by the composition formulas Y 3 Al 5 O 12 :Ce, (Y 0.8 Gd 0.2 ) 3 Al 5 O 12 :Ce, Y 3 (Al 0.8 Ga 0.2 ) 5 O 12 :Ce, and (Y,Gd) 3 (Al,Ga) 5 O 12 .
  • Other examples include phosphors in which the yttrium is partially or entirely substituted by terbium, lutetium, such as Tb 3 Al 5 O 12 :Ce and Lu 3 Al 5 O 12 :Ce.
  • phosphors include ZnS:Eu, Zn2GeO4:Mn, and MGa 2 S 4 :Eu (wherein M is at least one selected from strontium, calcium, barium, magnesium and zinc; and X is at least one selected from fluorine, chlorine, bromium, and iodine).
  • the abovementioned phosphors can also contain, instead of or in addition to europium, at least one selected from terbium, copper, silver, gold, chromium, neodymium, dysprosium, cobalt, nickel, and titanium.
  • a Ca-Al-Si-O-N based oxynitride glass phosphor is a phosphor constituted by an oxynitride glass as a matrix material, and comprising from 20 to 50 mol% CaCO 3 in terms of CaO, from 0 to 30 mol% Al2O3, from 25 to 60 mol% SiO, from 5 to 50 mol% AIN, and from 0.1 to 20 mol% of a rare earth oxide or transition metal oxide, the total of the five components being 100 mol%.
  • the phosphor constituted by an oxynitride glass as a matrix material contains no more than 15 weight% nitrogen, and the fluorescent glass preferably contains, apart from the rare earth oxide ion, from 0.1 to 10 mol% of another rare earth element ion constituting a sensitizer as a rare earth oxide as a co-activator.
  • a composition or silicone film according to the various embodiments of the present invention can be manufactured by mixing the composition according to the present invention and one or more of the inorganic particles and/or phosphors described above as necessary, and heating the obtained mixture for a comparatively short time to partially crosslink it.
  • the heating temperature is from 50 to 200°C or from 80 to 150°C.
  • the heating time is from 1 to 20 minutes or from 5 to 15 minutes.
  • the composition according to the present invention or the mixture forms a silicone film of the present invention that is partially crosslinked via a hydrosilylation reaction and is a solid with high hardness at room temperature, and that is a crosslinked product that softens or liquefies at high temperatures, such as 100°C or above.
  • the present invention also relates to a laminate comprising at least one layer containing the composition according to the present invention, e.g., a laminate comprising the silicone film and at least one other sheet.
  • the thickness of the laminate according to the present invention for example, from 10 ⁇ m to 10 mm, from 100 ⁇ m to 8 mm or from 0.5 to 5 mm.
  • the thickness of the other sheet when present, which may have the same thickness as the silicone film according to the present invention, or may be thinner, as necessary, in which case a thickness of, for example, from 0.1 ⁇ m to 3 mm or from 1 ⁇ m to 2 mm.
  • the other sheet when present, can be a supporter sheet for supporting the silicone film.
  • the supporter sheet may be a single-layer sheet, or a multi-layer sheet in which a plurality of films are layered.
  • the other sheet may also be a protective sheet for preventing dust from adhering to the silicone film.
  • the material of the supporter sheet there is no particular limitation upon the material of the supporter sheet as long as it is capable of supporting the silicone film.
  • the material of the protective sheet as long as it is capable of being peeled from the silicone film.
  • supporter sheet and protective sheet materials include polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyvinylidene chloride, polystyrene, polyvinyl alcohol, polyimide, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer resin, and cellulose triacetate.
  • a surface-treating agent such as a fluorine-containing release agent or a silicone-containing release agent may be applied to the surface of the supporter sheet or protective sheet.
  • the supporter sheet may be peeled off before or during compression molding or laminating.
  • the supporter sheet may be machined simultaneously with the silicone composition layer; in such cases, the sheet may be peeled off the silicone composition layer after machining, or may be left bonded to the silicone composition layer.
  • the other sheet when present, may comprise at least one type of non-hot melt curable silicone composition, such as those described in PCT Appl. No. PCT/US2013/077074, filed December 20, 2014 .
  • Mold Type-A A nano pillar pattern mold COP (cyclic olefin polymer) film FLP230/200/460-120 (phi 230 nm, pattern height 200 nm, pitch 400 nm, 0.2 mm film thick, purchased from Kyodo International, Inc).
  • Mold Type-B A random moth-eye pattern metal mold, (produced by Tokai Seimitsu Kogyo Co., LTD, pattern height: 212nm, pattern pitch: 130 nm).
  • Mold Type-C A Micro Mesh, (mesh count 325, wire diameter 280 ⁇ m).
  • the LED device described below in the various non-limiting examples was MA5050-A2, (Size: 50 x 50 mm, having 100 LED chips on the board) without white dome around LED chip area. Size of LED chip on the LED device MA5050 was 260 ⁇ m x 585 ⁇ m, 90 ⁇ m thick.
  • Table 1 summarizes the patterned s described in the various non-limiting examples presented herein.
  • Table 1 Example Number Hot melt silicone film # Pattern Size Pattern Shape Release Liner 6 1 Nano Pillar Patterned COP film (Mold Type A) 7 Nano Moth-eye Ethylene tetrafluoroethylene (ETFE) release film 1 patterned with Mold Type B 8 Micro Mesh Metal mesh (Mold Type-C) 9 Micro Mesh ETFE release film 2 patterned with Mold Type C 10 2 11 3 12 4 13 5 Ref. Ex. 1 1 No-pattern No mold ETFE release film
  • the flask is equipped with a thermometer, Teflon stir paddle, and a Dean Stark apparatus prefilled with toluene and attached to a water-cooled condenser. A nitrogen blanket is then applied. An oil bath is used to heat the flask at reflux for 30 minutes. Subsequently, the flask is cooled to about 108°C (pot temperature).
  • the capped siloxane is then added to the Phenyl-T Resin/toluene solution at 108°C and refluxed for about 2 hours.
  • the solution is then cooled to 90°C and 33.63 g of DI water is added.
  • the solution is then heated at reflux for one hour and water is removed via azeotropic distillation.
  • the solution is then heated for an additional 3 hours and then cooled to 100°C.
  • 4.8 grams of Darco G60 carbon black is added and the solution is cooled to room temperature with stirring and stirred overnight at room temperature. And then pressure filtered through a 5.0 ⁇ m filter to isolate the solid composition.
  • the solid composition 50.01 g, is then dissolved in toluene to form a 58.2% solids solution. 0.15 grams of a 1 weight percent DBU catalyst/toluene solution is then added and the solution is distilled at 30°C and 13 Torr for 2 hours to obtain 36.05 g (80.7% solid solution). Subsequently, this solution is cast at about 1 mm thickness on PET film, followed by drying under nitrogen over for 4 days. Excess solvent is then further removed under vacuum at 50°C for 2 hours in a vacuum oven. A hot melt silicone film 1 with thickness of 400 ⁇ m was obtained by pressing the solid composition at 80°C.
  • the obtained silicone composition was poured into a 1 cm-thick mold, heated in a press at 100°C for 30 minutes, and cooled, after which measurement of type A hardness at 25°C yielded a result of 68.
  • the obtained silicone composition was heated in a hot press at 100°C for 30 minutes to obtain a 400 micrometer-thick transparent hot melt silicone film 2.
  • a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (in an amount such that the amount of metallic platinum was 5 ppm in terms of mass with respect to the total amount of composition) was added and heated in a flask at 100°C for 6 hours. No silicon atom-bonded hydrogen atoms were detected via FT-IR, confirming the progress of the hydrosilylation reaction.
  • a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (in an amount such that the amount of metallic platinum was 5 ppm in terms of mass with respect to the total amount of composition) was added and heated in a flask at 100°C for 6 hours. No silicon atom-bonded hydrogen atoms were detected via FT-IR, confirming the progress of the hydrosilylation reaction.
  • the obtained solid hydrosilylation curable silicone composition was compressed using a 100°C press to obtain a 400 micrometer-thick hot melt silicone film 5.
  • a hot melt silicone film 1 was contacted on an LED device MA5050-A2 (Size: 50 x 50 mm, having 100 LED chips on the board, without white dome around LED chip area).
  • the LED device and the hot melt silicone film 1 were set in a vacuum laminator, (product name: Laminator 0505S, produced by Nisshinbo Mechatronics Inc.).
  • a patterned COP film (Mold Type-A) was positioned on the hot melt silicone film 1 with the pattern on COP film facing the hot melt silicone film 1. Then, air of the first chamber and the second chamber was vacuumed. As the second chamber was ventilated, the hot melt silicone film 1 was laminated on the LED device pressed by the patterned COP film at 135°C for 20 minutes.
  • Silicone encapsulant 1 on the LED device was obtained. After releasing the patterned COP film, weak blue or green light refection of special characteristic of nano patterned surface was observed on the silicone encapsulant 1. Surface of the silicone encapsulant 1 was scanned by SPM (Scanning Probe Microscope). Obtained SPM image showed that the surface has many nano size dimples. Cross section of the silicone encapsulant 1 was observed by SEM (Scanning Electron Microscope). The depth of the imprinted dimples was around 120 nm to 160 nm.
  • ETFE release film 1 was obtained by pressing A random moth-eye pattern metal mold (Mold Type B) on the ETFE release film by vacuum hot press at 150°C.
  • a hot melt silicone film 1 was contacted on an LED device MA5050-A2 (Size: 50 x 50 mm, having 100 LED chips on the board, without white dome around LED chip area).
  • the LED device and the hot melt silicone film 1 were set in a vacuum laminator, (product name: Laminator 0505S, produced by Nisshinbo Mechatronics Inc.).
  • the ETFE release film 1 was positioned on the hot melt silicone film 1 with the pattern of the ETFE release film 1 facing the hot melt silicone film 1. Then, air of the first chamber and the second chamber was vacuumed.
  • the hot melt silicone film 1 was laminated on the LED device pressed by ETFE release film 1 at 135°C for 20 minutes. Silicone encapsulant 2 on the LED device was obtained. After releasing the release film, imprinted surface pattern of the silicone encapsulant 2 was observed by SPM.
  • a hot melt silicone film 1 was contacted on an LED device MA5050-A2 (Size: 50 x 50 mm, having 100 LED chips on the board, without white dome around LED chip area).
  • the LED device and the hot melt silicone film 1 were set in a vacuum laminator, (product name: Laminator 0505S, produced by Nisshinbo Mechatronics Inc.).
  • a flat ETFE film was positioned on the hot melt silicone film 1. Then, air of the first chamber and the second chamber was vacuumed. As the second chamber was ventilated, the hot melt silicone film 1 was laminated on the LED device pressed by ETFE film at 135°C for 20 minutes. After releasing the ETFE film, the obtained LED assembly was cured in oven at 170°C for 3 hours.
  • a metal mesh (Mold Type-C) was put on the silicone encapsulant, then the mesh was pressed by the vacuum laminator at 135°C. After releasing the metal mesh, silicone encapsulant 3 in the LED assembly was obtained. Imprinted surface pattern of the silicone encapsulant 3 was observed by optical microscope.
  • ETFE release film 2 was obtained by pressing a micro mesh (Mold Type-C) on the ETFE release film by vacuum hot press at 150°C.
  • a hot melt silicone film 1 was contacted on an LED device MA5050-A2 (Size: 50 x 50 mm, having 100 LED chips on the board, without white dome around LED chip area).
  • the LED device and the hot melt silicone film 1 were set in a vacuum laminator, (product name: Laminator 0505S, produced by Nisshinbo Mechatronics Inc.).
  • the ETFE release film 2 was positioned on the hot melt silicone film 1 with the pattern of the ETFE release film 2 facing the hot melt silicone film 1. Then, air of the first chamber and the second chamber was vacuumed..
  • the hot melt silicone film 1 was laminated on the LED device pressed by the ETFE release film 2 at 135°C for 20 minutes. Silicone encapsulant 4 on the LED device was obtained. After releasing the release film, imprinted surface pattern of the silicone encapsulant 4 was observed by SPM.
  • the hot melt silicone film 2 was laminated on the LED device at 150°C for 10 minutes instead of the hot melt silicone film 1.
  • Silicone encapsulant 5 on the LED device was obtained. After releasing the release film, imprinted surface pattern of the silicone encapsulant 5 was observed by SPM.
  • the hot melt silicone film 3 was laminated on the LED device at 150°C for 10 minutes instead of the hot melt silicone film 1.
  • Silicone encapsulant 6 on the LED device was obtained. After releasing the release film, imprinted surface pattern of the silicone encapsulant 5 was observed by SPM.
  • the hot melt silicone film 3 was laminated on the LED device at 150°C for 10 minutes instead of the hot melt silicone film 4.
  • Silicone encapsulant 7 on the LED device was obtained. After releasing the release film, imprinted surface pattern of the silicone encapsulant 7 was observed by SPM.
  • the hot melt silicone film 5 was laminated on the LED device at 150°C for 10 minutes instead of the hot melt silicone film 5.
  • Silicone encapsulant 8 on the LED device was obtained. After releasing the release film, imprinted surface pattern of the silicone encapsulant 8 was observed by SPM.
  • the hot melt silicone film 1 was laminated by flat ETFE film instead of the patterned COP film. Silicone encapsulant 9 on the LED device was obtained. After releasing the ETFE film, flat surface of the silicone encapsulant 9 was observed by SPM.
  • Example 7 and Reference Example 1 were measured by HalfMoon, (produced by Otsuka Electronics Co., LTD). Before lamination process, LOP of LED devices used in Example 7 and Reference Example 1 were 1740 and 1744 mW at electric current 700 mA, respectively. After the lamination, those were 1772 and 1762, respectively. LOP ratio (LOP after lamination / before lamination) was calculated. LOP of LED assembly in Example 7 was better than that in Reference Example 1. Table 2 Reference Example 1 Example 7 LOP before lamination (mW) 1744 1740 LOP after lamination (mW) 1762 1772 Ratio of LOP (after lamination/before lamination) (%) 101.0 101.8
  • a reactor includes a plurality of reactors, such as in a series of reactors.
  • the term “or” is used to refer to a nonexclusive or, such that "A or B” includes “A but not B,” “B but not A,” and “A and B,” unless otherwise indicated.
  • the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed step of doing X and a claimed step of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Led Device Packages (AREA)

Claims (15)

  1. Une méthode de réalisation d'un ensemble optique, comprenant :
    le fait d'assujettir un dispositif optique dans une installation, le dispositif optique présentant une surface optique, où un film de silicone est positionné par rapport à la surface optique, le film de silicone présentant une surface distale relativement à la surface optique ;
    le fait de positionner un revêtement de séparation avec une surface de revêtement faisant face au film de silicone, le revêtement de séparation incluant une empreinte sur la surface de revêtement ; et
    le fait de presser le revêtement de séparation contre le film de silicone, causant de ce fait la transmission de l'empreinte du revêtement de séparation à la surface distale du film de silicone créant une empreinte de surface dans la surface distale.
  2. La méthode de la revendication 1, où le film de silicone comprend une composition thermofusible contenant de la silicone.
  3. La méthode de la revendication 2, où la composition thermofusible contenant de la silicone comprend un copolymère bloc d'organosiloxane.
  4. La méthode de la revendication 3, où le copolymère bloc d'organosiloxane comprend :
    de 40 à 90 % en moles d'une unité disiloxy représentée par [R6 2SiO2/2] ;
    de 10 à 60 % en moles d'une unité trisiloxy représentée par [R7SiO3/2] ; et
    de 2 à 25 % en moles d'un groupe silanol représenté par [=SiOH] ;
    chaque R6 représentant indépendamment un groupe hydrocarboné en C1 à C30 ;
    chaque R7 représentant indépendamment un groupe hydrocarboné en C1 à C20 ;
    l'unité disiloxy [R6 2SiO2/2] étant présente dans un bloc à chaîne linéaire comprenant une moyenne de 50 à 300 unités disiloxy [R6 2SiO2/2] ;
    l'unité trisiloxy étant présente dans un bloc à chaîne non linéaire présentant une masse moléculaire d'au moins 500 g/mol ; et
    chaque bloc à chaîne linéaire étant lié à au moins un bloc à chaîne non linéaire.
  5. La méthode de la revendication 1, où le film de silicone comprend une composition thermofusible contenant de la silicone sélectionnée dans le groupe constitué de :
    (1) une composition de silicone durcissable par hydrosilylation qui n'a pas réagi ;
    (2) une composition de silicone durcissable par hydrosilylation obtenue par réticulation partielle d'une composition de silicone durcissable par hydrosilylation qui n'a pas réagi ; et
    (3) une composition de silicone durcissable par hydrosilylation comprenant : un produit réticulé présentant des atomes d'hydrogène liés à un atome de silicium et/ou des groupes alcényle ; et au moins un type de constituant réactif par hydrosilylation, le produit réticulé étant obtenu par réticulation d'une composition de silicone réactive par hydrosilylation qui n'a pas réagi.
  6. La méthode de la revendication 5, où le film de silicone comprend une composition thermofusible contenant de la silicone comprenant :
    (A) au moins un type d'organopolysiloxane qui est solide à 25 °C et présente en moyenne plus de deux groupes alcényle dans une molécule ;
    (B) au moins un type d'organopolysiloxane contenant au moins deux atomes d'hydrogène liés à un atome de silicium dans une molécule, dans une quantité telle qu'un rapport d'une concentration molaire totale d'atomes d'hydrogène liés à un atome de silicium à une concentration molaire totale de groupes alcényle dans le constituant (A) soit compris dans un intervalle de 0,2 à 4 ; et
    (C) un catalyseur d'hydrosilylation dans une quantité suffisante pour effectuer une réaction d'hydrosilylation.
  7. La méthode de la revendication 5, où le film de silicone comprend une composition thermofusible contenant de la silicone comprenant une composition de silicone durcissable par hydrosilylation (2) obtenue par réticulation partielle d'une composition de silicone durcissable par hydrosilylation qui n'a pas réagi obtenue par l'arrêt d'une réaction d'hydrosilylation à une conversion allant de 50 à 95 % d'une composition de silicone réactive par hydrosilylation comprenant :
    (D) au moins un type d'organopolysiloxane présentant en moyenne plus de deux groupes alcényle dans une molécule ;
    (E) au moins un type d'organopolysiloxane présentant au moins deux atomes d'hydrogène liés à un atome de silicium dans une molécule, dans une quantité telle qu'un rapport d'une concentration molaire totale d'atomes d'hydrogène liés à un atome de silicium à une concentration molaire totale de groupes alcényle dans le constituant (D) soit compris dans un intervalle de 0,2 à 4 ; et
    (F) un catalyseur d'hydrosilylation dans une quantité suffisante pour effectuer une réaction d'hydrosilylation.
  8. La méthode de la revendication 7, où le constituant (D) comprend un mélange de :
    (D-1) un organopolysiloxane représenté par la formule d'unité moyenne suivante :

            (R1 3SiO1/2)a(R1 2SiO2/2)b (R1SiO3/2)cSiO4/2)dR2O1/2)e

    où R1 est un groupe phényle, un groupe alkyle ou groupe cycloalkyle présentant de 1 à 6 carbones, ou un groupe alcényle présentant de 2 à 6 carbones, à condition que de 60 à 80 % en moles de R1 soient des groupes phényle et que de 10 à 20 % en moles de R1 soient des groupes alcényle ; R2 est un atome d'hydrogène ou un groupe alkyle présentant de 1 à 6 carbones ; et « a », « b », « c », « d », et « e » sont des nombres qui satisfont : 0 ≤ a ≤ 0,2, 0,2 ≤ b ≤ 0,7, 0,2 ≤ c ≤ 0,6, 0 ≤ d ≤ 0,2, 0 ≤ e ≤ 0,1, et a+b+c+d = 1 ; et
    (D-2) un organopolysiloxane représenté par la formule générale suivante :

            R3 3SiO(R3 2SiO)mSiR3 3

    où R3 est un groupe phényle, un groupe alkyle ou groupe cycloalkyle présentant de 1 à 6 carbones, ou un groupe alcényle présentant de 2 à 6 carbones, à condition que de 40 à 70 % en moles de R3 soient des groupes phényle et qu'au moins un R3 soit un groupe alcényle ; et « m » est un entier allant de 5 à 100, dans une quantité de ce constituant qui va de 0 à 20 parties en poids pour 100 parties en poids du constituant (D-1).
  9. La méthode de la revendication 5, où la composition de silicone durcissable par hydrosilylation (3) comprend :
    (G) un produit réticulé contenant un groupe alcényle obtenu par réaction d'hydrosilylation d'une composition de silicone réactive par hydrosilylation qui n'a pas réagi comprenant :
    (G-1) au moins un type d'organopolysiloxane présentant en moyenne plus de deux groupes alcényle dans une molécule ;
    (G-2) au moins un type d'organopolysiloxane présentant au moins deux atomes d'hydrogène liés à un atome de silicium dans une molécule, dans une quantité telle qu'un rapport d'une concentration molaire totale d'atomes d'hydrogène liés à un atome de silicium à une concentration molaire totale de groupes alcényle dans le constituant (G-1) soit compris dans un intervalle de 0,3 à 0,9 ; et
    (G-3) un catalyseur d'hydrosilylation dans une quantité suffisante pour effectuer une réaction d'hydrosilylation ; et
    (H) au moins un type d'organopolysiloxane présentant au moins deux atomes d'hydrogène liés à un atome de silicium dans une molécule, dans une quantité telle qu'un rapport d'une concentration molaire totale d'atomes d'hydrogène liés à un atome de silicium à une concentration molaire totale de groupes alcényle dans le produit réticulé soit compris dans un intervalle de 0,1 à 2,0.
  10. La méthode de la revendication 9, où l'une des conditions suivantes est satisfaite :
    (G-1) est un organopolysiloxane présentant en moyenne plus de deux groupes alcényle dans une molécule et représenté par la formule de composition moyenne suivante :

            R4 xSiO(4-x)/2

    où R4 représentent chacun indépendamment un groupe hydrocarboné monovalent substitué ou non substitué, à condition que de 0,1 à 40 % en moles de R4 soient des groupes alcényle ; et « x » est un nombre positif qui satisfait : 1 ≤ x < 2 ;
    (G-2) est un diorganopolysiloxane représenté par la formule générale suivante :

            HR5 2Si(R5 2SiO)nR5 2SiH

    où R5 représentent chacun indépendamment un groupe hydrocarboné monovalent substitué ou non substitué ne présentant pas de liaison insaturée aliphatique, et « n » est un entier allant de 0 à 1 000 ; et
    (H) est un organohydrogénopolysiloxane représenté par la formule de composition moyenne suivante :

            R5 yHzSiO(4-y-z)/2

    où R5 est tel que défini ci-dessus, et « y » et « z » sont des nombres positifs qui satisfont : 0,7 ≤ y ≤ 2,1, 0,001 ≤ z ≤ 1,0, et 0,8 ≤ y+z ≤ 2,6.
  11. La méthode de la revendication 1, comprenant en sus le fait d'appliquer de la chaleur avec une source de chaleur sur le film de silicone afin de stratifier le film de silicone sur le dispositif optique.
  12. Un ensemble optique incluant un dispositif optique présentant une surface optique et un film de silicone disposé sur la surface optique, le film de silicone présentant une surface pourvue d'une empreinte sur une surface distale de la surface optique, créé par un procédé comprenant :
    le fait d'assujettir le dispositif optique dans une installation, où le film de silicone est positionné par rapport à la surface optique ;
    le fait de positionner un revêtement de séparation avec une surface de revêtement faisant face au film de silicone, le revêtement de séparation incluant une empreinte sur la surface de revêtement ; et
    le fait de presser le revêtement de séparation contre le film de silicone, causant de ce fait la transmission de l'empreinte du revêtement de séparation à la surface distale du film de silicone créant la surface pourvue d'une empreinte dans la surface distale.
  13. L'ensemble optique de la revendication 12, comprenant en sus le fait d'appliquer de la chaleur avec une source de chaleur sur le film de silicone afin de stratifier le film de silicone sur le dispositif optique.
  14. Un système pour la réalisation d'un ensemble optique, comprenant :
    une installation configurée afin d'assujettir un dispositif optique et de permettre le positionnement d'un film de silicone par rapport à la surface optique ;
    un revêtement de séparation avec une surface de revêtement configurée afin de faire face au film de silicone, le revêtement de séparation incluant une empreinte sur la surface de revêtement ; et
    un mécanisme de pression configuré afin de presser le revêtement de séparation contre le film de silicone, causant de ce fait la transmission de l'empreinte du revêtement de séparation à la surface distale du film de silicone créant une surface pourvue d'une empreinte dans la surface distale.
  15. Le système de la revendication 14, comprenant en sus une source de chaleur configurée afin d'appliquer de la chaleur sur le film de silicone afin de stratifier le film de silicone sur le dispositif optique.
EP15747594.8A 2014-06-04 2015-06-04 Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques Active EP3152619B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462007554P 2014-06-04 2014-06-04
PCT/US2015/034113 WO2015187909A1 (fr) 2014-06-04 2015-06-04 Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques

Publications (2)

Publication Number Publication Date
EP3152619A1 EP3152619A1 (fr) 2017-04-12
EP3152619B1 true EP3152619B1 (fr) 2018-03-28

Family

ID=53783898

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15747594.8A Active EP3152619B1 (fr) 2014-06-04 2015-06-04 Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques

Country Status (7)

Country Link
US (1) US9853193B2 (fr)
EP (1) EP3152619B1 (fr)
JP (1) JP2017520918A (fr)
KR (1) KR20170016889A (fr)
CN (1) CN106462056A (fr)
TW (1) TW201609350A (fr)
WO (1) WO2015187909A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3152619B1 (fr) 2014-06-04 2018-03-28 Dow Corning Corporation Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques
WO2018112702A1 (fr) * 2016-12-19 2018-06-28 陈强 Dispositif de traitement de revêtement thermofusible
TWI762649B (zh) * 2017-06-26 2022-05-01 日商杜邦東麗特殊材料股份有限公司 黏晶用固化性矽組合物
TW201911610A (zh) * 2017-07-27 2019-03-16 美商羅門哈斯電子材料有限公司 聚矽氧組合物及控制光之物件
TWI787326B (zh) * 2017-09-08 2022-12-21 日商杜邦東麗特殊材料股份有限公司 密封光半導體元件的製造方法
JP7017359B2 (ja) * 2017-09-29 2022-02-08 Hoya株式会社 光半導体装置
JP7087116B2 (ja) * 2018-06-08 2022-06-20 エルケム・シリコーンズ・シャンハイ・カンパニー・リミテッド 硬化性シリコーン組成物
JP7037070B2 (ja) * 2019-01-11 2022-03-16 日亜化学工業株式会社 発光装置の製造方法
JP7260828B2 (ja) * 2019-01-11 2023-04-19 日亜化学工業株式会社 発光装置
US11437551B2 (en) * 2019-03-19 2022-09-06 Seoul Viosys Co., Ltd. Light emitting device package and application thereof
DE102019109586A1 (de) * 2019-04-11 2020-10-15 Osram Opto Semiconductors Gmbh Elektronisches bauelement und verfahren zur montage eines elektronischen bauelements
JP2021161400A (ja) * 2020-03-30 2021-10-11 ダウ・東レ株式会社 硬化性ホットメルトシリコーン組成物、その硬化物、及び前記組成物又は硬化物を含む積層体
EP3929658A1 (fr) * 2020-06-23 2021-12-29 Koninklijke Philips N.V. Procédé d'impression et couche à motifs

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08255806A (ja) * 1995-03-17 1996-10-01 Toshiba Corp 樹脂封止型半導体装置の製造方法
US6183929B1 (en) * 1999-08-02 2001-02-06 Xerox Corporation Functional fusing agent
JP2007502886A (ja) * 2003-08-20 2007-02-15 ダウ・コーニング・コーポレイション カルバゾリル官能基含有ポリシロキサン樹脂、シリコーン組成物、及び有機発光ダイオード
JP2006063092A (ja) * 2004-07-29 2006-03-09 Dow Corning Toray Co Ltd 硬化性オルガノポリシロキサン組成物、その硬化方法、光半導体装置および接着促進剤
JP4519762B2 (ja) * 2005-11-21 2010-08-04 リンテック株式会社 樹脂封止型半導体装置の製造方法
CN101393391B (zh) * 2008-11-06 2011-02-16 上海交通大学 纳米压印装置
SG172062A1 (en) * 2009-01-08 2011-07-28 Asahi Glass Co Ltd Mold-releasing film and method for manufacturing light emitting diode
JP2012061599A (ja) 2009-01-21 2012-03-29 Nissan Chem Ind Ltd ベンゾシクロブテン樹脂のインプリント技術への適用及び当該技術によるパターン形成方法
JP5190996B2 (ja) * 2009-02-17 2013-04-24 日東電工株式会社 光半導体封止用シート
JP5671302B2 (ja) * 2009-11-10 2015-02-18 富士フイルム株式会社 インプリント用硬化性組成物、パターン形成方法およびパターン
WO2011088588A1 (fr) * 2010-01-20 2011-07-28 Honeywell International, Inc. Réacteur utilisable en vue d'une analyse quantitative d'acides nucléiques
JP2013004734A (ja) * 2011-06-16 2013-01-07 Asahi Glass Co Ltd 発光装置
JP5992666B2 (ja) * 2011-06-16 2016-09-14 東レ・ダウコーニング株式会社 架橋性シリコーン組成物及びその架橋物
TWI556473B (zh) * 2011-11-28 2016-11-01 隆達電子股份有限公司 發光二極體封裝及製作發光二極體封裝之方法
US9006006B2 (en) * 2011-11-29 2015-04-14 Sharp Kabushiki Kaisha Manufacturing method for light-emitting device comprising multi-step cured silicon resin
WO2013109607A1 (fr) 2012-01-16 2013-07-25 Dow Corning Corporation Article optique et procédé de formation
US8841689B2 (en) * 2012-02-03 2014-09-23 Shin-Etsu Chemical Co., Ltd. Heat-curable silicone resin sheet having phosphor-containing layer and phosphor-free layer, method of producing light emitting device utilizing same and light emitting semiconductor device obtained by the method
EP2827361A4 (fr) * 2012-03-12 2015-04-15 Asahi Kasei E Materials Corp Moule, stratifié de réserve et procédé de fabrication associé, et structure à microrelief
JP6139515B2 (ja) * 2012-05-25 2017-05-31 リンテック株式会社 ダイシングシート
JP6046395B2 (ja) * 2012-06-29 2016-12-14 東レ・ダウコーニング株式会社 反応性シリコーン組成物、反応性熱可塑体、硬化物、および光半導体装置
JP5960014B2 (ja) * 2012-09-28 2016-08-02 日東電工株式会社 蛍光接着シート、光半導体素子−蛍光体層感圧接着体および光半導体装置
JP6070498B2 (ja) * 2012-12-21 2017-02-01 信越化学工業株式会社 蛍光体含有層と白色顔料含有層を有する熱硬化性シリコーン樹脂シート、それを使用する発光装置の製造方法及び封止発光半導体装置
CA2907398A1 (fr) * 2013-03-15 2014-09-18 Gary W. Jones Dispositif de conversion de spectre de lumiere ambiante
EP3152619B1 (fr) 2014-06-04 2018-03-28 Dow Corning Corporation Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques

Also Published As

Publication number Publication date
JP2017520918A (ja) 2017-07-27
US20170092822A1 (en) 2017-03-30
US9853193B2 (en) 2017-12-26
WO2015187909A1 (fr) 2015-12-10
TW201609350A (zh) 2016-03-16
CN106462056A (zh) 2017-02-22
KR20170016889A (ko) 2017-02-14
EP3152619A1 (fr) 2017-04-12

Similar Documents

Publication Publication Date Title
EP3152619B1 (fr) Procede d&#39;impression de composition silicone durcissable de type thermofusible pour dispositifs optiques
EP2935494B1 (fr) Composition de silicone pouvant durcir du type thermofusible pour le moulage par compression ou la stratification
JP6707516B2 (ja) 硬化性粒状シリコーン組成物、およびその製造方法
CN109689791B (zh) 固化性粒状硅组合物、由其构成的半导体用构件及其成型方法
EP2936581B1 (fr) Structures polyméres multicouches et méthodes
US10167418B2 (en) Hot melt silicone and curable hot melt composition
TWI814741B (zh) 硬化性聚矽氧組成物、由其構成之光學構件用樹脂片及發光裝置
CN113330071B (zh) 固化性有机硅组合物、其固化物及其制造方法
EP3190156A1 (fr) Composition de silicone durcissable, silicone thermofusible durcissable, et dispositif optique
JPWO2018030286A1 (ja) 硬化性粒状シリコーン組成物、それからなる光反射材、およびその製造方法
CN113631660B (zh) 固化性有机硅组合物、其固化物及其制造方法
JP7032052B2 (ja) シリコーン樹脂フィルムおよびその製造方法、並びに半導体デバイスの製造方法
CN113614174B (zh) 固化性有机硅组合物、其固化物及其制造方法
CN113396042A (zh) 具有热熔性的固化性有机硅片材的制造方法
JP7509756B2 (ja) 硬化性シリコーン組成物、その硬化物、およびその製造方法
JP7509755B2 (ja) 硬化性シリコーン組成物、その硬化物、およびその製造方法

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161201

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20171102

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 983952

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180415

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015009385

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180628

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180328

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180628

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 983952

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180730

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015009385

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190103

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180630

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180604

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180630

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180630

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180604

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180630

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180604

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20190604

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190604

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602015009385

Country of ref document: DE

Representative=s name: MURGITROYD & COMPANY, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 602015009385

Country of ref document: DE

Owner name: DOW TORAY CO., LTD., JP

Free format text: FORMER OWNERS: DOW CORNING CORPORATION, MIDLAND, MICH., US; DOW CORNING TORAY CO., LTD., TOKYO, JP

Ref country code: DE

Ref legal event code: R081

Ref document number: 602015009385

Country of ref document: DE

Owner name: DOW CORNING CORP., MIDLAND, US

Free format text: FORMER OWNERS: DOW CORNING CORPORATION, MIDLAND, MICH., US; DOW CORNING TORAY CO., LTD., TOKYO, JP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150604

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180328

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180728

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230526

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230412

Year of fee payment: 9